Aldol condensation using cobalt II halide hydrazine complexes

ABSTRACT

Cobalt (II) halide trihydrazinates of the formula

United States Patent Stapler et al.

[451 May 20, 1975 ALDOL CONDENSATION USING COBALT II I-IALIDE HYDRAZINECOMPLEXES Inventors: Christian H. Stapfer, Newton;

Richard W. DAndrea, New Hope, both of Pa.

Cincinnati Milacron Chemicals, Inc., Reading, Ohio Filed: Sept. 16, 1971Appl. No.: 181,214

Related US. Application Data Division of Ser. No. 26,161, April 6, 1970,Pat. No. 3,728,087.

Assignee:

US. Cl 260/586 C; 260/590; 260/593; 260/594 Int. Cl C07c 45/00; C07c49/04 Field of Search... 260/586 C, 590, 594, 593 R; 423/413, 462

References Cited UNITED STATES PATENTS Metzweiller 260/586 C Daniels260/439 R Stoffer et al. 260/439 R Haslam 260/586 C OTHER PUBLICATIONSNicholls et al.: I-lydrazine Complexes of Cobalt (II) Chloride, J. Chem.Soc. (A) 1966, pp. 950-952.

Primary Examiner-Oscar R. Vertiz Assistant Examiner-Gary P. StraubAttorney, Agent, or FirmCushman, Darby and Cushman [57] ABSTRACT Cobalt(II) halide trihydrazinates of the formula complexes of the formula[Co(II) (R NH NH X also have these same uses.

9 Claims, No Drawings ALDOL CONDENSATION USING COBALT ll HALIDEHYDRAZINE COMPLEXES This is a division of application Ser. No. 26,161,filed Apr. 6, l970, now U.S. Pat. No. 3,728,087.

This invention relates to novel cobalt complexes and their use in dryingalkyd coating compositions, autoxidation of olefinic materials and inketone aldol condensations.

Hydrazines are known to form stable coordination complexes, or chelates,with transition metals. With cobaltous halides they form 2 to 1complexes known as the dihydrazinates which are described in theliterature. Hydrazine itself reacts readily with cobalt (ll) chloride,for instance to form the dihydrazinate complex: {Co(ll) (N H,) ]Cl andunder certain conditions, the unstable hexahydrazinate [Co(ll) (N- H ]Clcan be formed in which the hydrazine acts as a unidentate ligand.

The term paint" is used herein to include oil-based paint, water-basedand organic-based varnishes, lacquers and similar coating compositionswhich may be clear, pigmented, or contain dyes.

The curing or drying of coating compositions such as alkyd paintformulations is frequently catalyzed by various metal salts. Cobaltsoaps are especially preferred as paint dryers because they mostactively promote the formation of free radicals at loci of unsaturationin films of coatings and paint. The production of these free radicalscatalyze an autoxidation process resulting in actual crosslinking withinthe film. However, cobalt salts have had several disadvantages prior tomy inven tion. In addition to high cost, cobalt salts cause extensivewrinkling in paint films when used in amounts necessary to producecommercially desirable drying times. It has been usually necessary toreplace a portion of the cobalt salt with a salt of a less expensivemetal because of the high cost and in order to prevent wrinkling, thereplacement of the amount of cobalt salt necessary to prevent wrinklingresults in a substantial increase in the time required for drying.Attempts have been made to accelerate the drying of alkyd paints byincluding compounds such as l,l-phenanthroline, 2,2'-bipyridine or8-hydroxyquinoline. While these accelerators have been used for cobaltand manganese drying catalysts, they have not attained significantcommercial importance. Although they may be good accelerators, thesecompounds are far too expensive to be used in the necessary amounts andalso promote discoloration of the paint film. For example,1,10-phenanthroline cannot be used in quantities exceeding 0.05 weightper cent of the paint because higher concentrations cause the paint filmto yellow and when used in levels of 0.05 weight per cent, theacceleration of drying time is not sufficient to off-set the increase incost.

Hydrazines have also been proposed as activators in drying alkyd paintsbut they cause extreme discoloration (yellowing), surface wrinkling anddeterioration. Moreover. they are not as active as would be desired.

It is also well known that the crosslinking polymerization of olefinicpolymers such as styrene or butadiene modified polyester resins proceedby oxygen transfer using organic peroxides as a source of free radicaland the same cobalt carboxylates as above as cocatalysts. Althoughcobalt soaps are the preferred cocatalysts for the polymerization ofthese resins, mainly because they allow good curing characteristics anddimensional stability. the time span in which they cause the polymericresin to gel is long and, should one want to reduce said time span byincreasing the amount of cobalt, they have a tendency to severelydiscolor the resin.

Furthermore, in various applications where the polyester resinformulation contains water, cobalt carboxylates are altogetherinadequate to promote crosslinking.

The use of various pyridine compounds including 2- pyridine aldazine hasbeen proposed as accelerators for cobalt and other driers in WheelerU.S. Pat. No. 2,961,331. However, the pyridine aldehydes required tomake the azines are expensive. Furthermore, it was considered essentialto have the pyridine nucleus present.

It is an object of the present invention to prepare novel trihydrazinecobalt complexes.

Another object is to prepare novel cobalt trihydrazinate hydrochloridecomplexes.

A further object is to provide novel driers for drying alkyd coatingcompositions and unsaturated polyesters.

An additional object is to provide a novel procedure for preparingketone aldol condensations.

It has now been found that these objects can be attained by preparingnovel cobalt ll halide trihydrazinates of the formula (1) [CO(ll) (RNHNH);,]X or 0 (N2H4 lal z where R is H, alkyl, aralkyl, aryl or haloaryland X is halogen and the use of these compounds or the known cobalt lldihydrazinates of the formula for curing drying alkyd resins and ascuring agents in other oxidative polymerization reactions such ascrosslinking of olefin polymer systems, particularly unsaturatedpolyesters initiated by organic peroxides. The compounds of the presentinvention are preferably employed as the sole cobalt source in suchcuring systems, but they can be replaced in part, e.g. up to percent, byconventional cobalt driers, e.g. cobalt 2- ethylhexoate, cobaltnaphthenate, cobalt neodecanoate, cobalt resinate, etc.

The compounds of the present invention of formulae (1) and (2), as wellas the old compounds of formula (3), are also useful as catalysts in thealdol condensation of ketones.

The compounds of the present invention are extremely sensitive to heatand oxidation and preferably are stored in an inert atmosphere, e.g.nitrogen, helium or argon at a low temperature, e.g. 0C. Since in manyinstances the bromides and iodides tend to decompose violently whenexposed to air, it is preferred to employ the chlorides.

It has been found that under anhydrous conditions, hydrazines react with2,2'-bipyridyl cobalt (ll) halide complexes to form, by liganddisplacement, quantitative amounts of the corresponding cobalt (ll)halide trihydrazinate complexes, a typical equation being "l (B pyH hSolvent 00 -z 4):sl 2

As stated, many of these new complexes have limited stability, tend tobecome pyrophoric when exposed to While not being limited to theory, itis believed that the reason why the excessive stoichiometry is needed inthe reaction above is that, in order to obtain the trishydrazinatehydrochloride, one first forms the unstable hexahydrazinatehydrochloride, an unidentate complex which, upon ligand displacement,leads to the desired chelate and free hydrazine hydrochloride:

As opposed to the well known tetrahedral or planar configuration of thecobalt (ll) halide dihydrazinates in which the cobalt is tetracoordinate(FIG. 1A), the new trihydrazinates and trihydrazinates-hydrochloridesare believed to have an octahedral Werner configuration with the hexacoordinated cobalt (FIG. lb).

u- ---u Co (1:)001

Planar configuration of (coal) (mm-mp ct Fig. 1a

1 /azm' fi octahedral. configuration of [cot-1i) (R-NH-Nflikjtil r1 lbWhether in their anhydrous solid form or in solution in various organicsolvents such as ketones, aldehydes, amides, esters, alcohols or amines,the cobalt (II) halido dihydrazinates and, to a higher degree,trihydrazinates have been found to be very potent catalysts in variouschemical processes involving oxygen transfer reactions. Typical solventswhich can be used to dissolve the chelates mentioned above are:cyclohexanone, benzaldehyde, dimethyl formamide, dimethyl sulfoxide,n-propyl alcohol, propylene glycol, methylacetoacetate, aceticanhydride, N,N, dimethyl aniline, acetone, methyl ethyl ketone, methylamyl ketone, isophorone, diethyl ketone, di-n-propyl ketone, diisopropylketone, di-n-butyl ketone, diisobutyl ketone, di sec butyl ketone,di-t-butyl ketone, di-n-amyl ketone, methyl-n-propyl ketone, pinacolone,6-methyl2- heptanone, methyl n-octyl ketone, ethyl n-butyl ketone,l-hydroxy-Z-propanone, 3-hydroxy-2-butanone, diacetone alcohol,cyclobutanone, cyclohexanonc, 2- methyl cyclohexanone, cycloheptanone,fenchone, acetophenone, benzophenone (molten), biacetyl. acctylpropionyl, acetyl acetone, mesityl oxide, hexanone-3. furfural,acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde,valeraldehyde, heptaldehyde, glyoxal, o-chlorobenzaldehyde,p-tolualdehyde, salicya laldehyde, phenylacetaldehyde,tetrahydrofurfural, glutaraldehyde, anline, N,N-diethyl aniline,N-methyl aniline, propyl amine, isopropyl amine, butyl amine, decylamine, diethyl amine, dipropyl amine, diisobutyl amine, diamyl amine,methyl ethyl amine, triethyl amine, tributyl amine, ethylene diamine,cyclohexyl amine, dicyclohexylamine, otoluidine, p-toluidine,mtoluidine, p-2-xylidene, o-chloroaniline, p-phenetidine, N-ethylaniline, dimethyl acetamide, isopropyl alcohol, ethyl alcohol, methylalcohol, butyl alcohol, sec. butyl alcohol, hexyl alcohol, isooctylalcohol, 2 ethylhexanol, n-octyl alcohol, decyl alcohol, isodecylalcohol, dodecyl alcohol, ethylene glycol, glycerine, dipropyleneglycol, diethylene glycol, mono butyl ether of diethylene glycol,hexamethylene glycol, polyethylene glycol molecular weight average 500,propionic anhydride, ethyl acetate, propyl acetate, amyl acetate, benzylacetate, butyl acetate, cyclohexyl acetate, phenyl acetate, ethylpropionate, methyl butyrate, amyl valerate, heptyl laurate, ethylpalmitate, diethyl oxalate, dimethyl malonate, dimethyl adipate, diethylsebacate, butyl lactate, methyl benzoate, ethyl benzoate, dioctylphthalate, dibutyl phthalate, methyl salicylate, ethyl acetoacetate,phenyl acetoacetate.

In making the compounds of formula (1), there are employed cobalt llbipyridine complexes such as cobalt (II) bipyridine difluoride, cobalt(II) bipyridine dichloride, cobalt (II) bipyridine dibromi'de, cobalt(II) bipyr idine diiodide. As hydrazines there can be used hydrazine,phenyl hydrazine, p-tolyl hydrazine, methyl hydrazine, allyl hydrazine,isopropyl hydrazine, nhexadecyl hydrazine, octadecyl hydrazine,cyclohexyl hydrazine, benzyl hydrazine, 2-naphthyl hydrazine, 2-chlorophenyl hydrazine, phenylethyl hydrazine, 4- bromophenyl hydrazine,2-fluorophenyl hydrazine, 2,4-dichlorophenyl hydrazine, octyl hydrazine,pethylphenyl hydrazine.

Any desired solvent can be used such as those set forth above.

Examples of compounds within formula (1) (cobalt always having a valenceof 2) are cobalt trihydrazinate dichloride, cobalt trihydrazinatedifluoride, cobalt trihydrazinate dibromide, cobalt trihydrazinatediiodide, cobalt tris(phenylhydrazinate) difluoride, cobalttris(phenylhydrazinate) dichloride, cobalt tris(phenylhydrazinate)dibromide, cobalt tris(phenylhydrazinate) diiodide, cobalttris(p-tolylhydrazinate) dichloride, cobalt tris (o-tolylhydrazinate)dibromide, cobalt tris (methylhydrazinate) dichloride, cobalt tris(ethylhydrazinate) dibromide, cobalt tris (allylhydrazinate) dichloride,cobalt tris (isopropyl hydrazinate) dichloride, cobalt tris (n-hexadecylhydrazinate) dichloride, cobalt tris (n-octadecylhydrazinate)dichloride, cobalt tris (cyclohexylhydrazinate) dichloride, cobalt tris(benzylhydrazinate) dichloride, cobalt tris (2-naphthylhydrazinate)dichloride, cobalt tris (2-chlorophenylhydrazinate) dichloride, cobalttris ('phenylethylhydrazinate) dichloride, cobalt tris(4-bromophenylhydrazinate) dichloride, cobalt tris(2-fluorophenylhydrazinate) dichloride, cobalt tris (2,4-dichlorophenylhydrazinate) dichloride, cobalt tris (octylhydrazinate)dichloride and cobalt tris (p-ethylphenylhydrazinate) dichloride.

In making the compounds of formula (2), there are employed cobalt (ll)halides such as cobalt (ll) fluoride, cobalt (ll) chloride, cobalt (ll)bromide and cobalt (ll) iodide together hydroxylamine hydrochloride,hydroxylamine hydrobromide and hydroxylamine hydroiodide together with ahydrazone. Examples of hydrazones include p-bromoacetophenone hydrazone,acetaldehyde hydrazone, benzal hydrazone, pmethylbenzal hydrazone,o-tolual hydrazone, benzophenone hydrazone, acetophenone hydrazone,valeraldehyde hydrazone, cyclohexanone hydrazone, acetone hydrazone,benzophenone hydrazone, furfural hydrazone, pentanone-3-hydrazone,butanone-2- hydrazone, heptadecanone-9-hydrazone,pentacosanone-3-hydrazone, isobutyraldehyde hydrazone, nbutyraldehydehydrazone, propional hydrazone, octaldehyde hydrazone, stearaldehydehydrazone.

Examples of compounds within formula (2) (cobalt always having a valenceof 2) are cobalt chloride trihydrazinate hydrochloride, cobalt bromidetrihydrazinate hydrochloride, cobalt iodide trihydrazinatehydrochloride, cobalt fluoride trihydrazinate hydrochloride, cobaltbromide trihydrazinate hydrobromide, cobalt iodide trihydrazinatehydroiodide.

The old cobalt ll halide dihydrazine complexes within formula (3) whichcan also be used as catalysts in the present invention can be made byconventional processes such as those disclosed in Audrieth et al., TheChemistry of Hydrazine (Wiley, 1951), Ahmad et al., Z. Anorg. Chem. Vol.330, pages 210-216 (1964); Nicholls et al., J. Chem. Soc. (A) (1966)pages 950-952; Clemens ct al., lnorg. Chem. (1963), Vol. 2, page 1251and Nicholls et al., J. Chem. Soc. (1964), page 4204.

Examples of compounds within formula (3) (cobalt always having a valenceof 2) are cobalt chloride dihydrazinate, cobalt bromide dihydrazinate,cobalt chloride di(phenylhydrazinate), cobalt bromidedi(phe'nylhydrazinate). cobalt chloride di(methylhydrazinate).

The compounds of formulae (1) and (2) appear to impart faster curingthan the comparable compounds of formula (3 The polymerization ofunsaturated polyesters by a crosslinking process is known to occur byfree radical initiation and this is usually achieved by using organic.

peroxides as polymerization catalysts. While the rate of decompositionof such peroxides into free radicals is influenced by the type ofperoxide and the temperature used, it is also directly influenced by theaddition of accelera'tors or inhibitors. Accelerators promote thedecomposition of peroxides into free radicals at temperatures belowthose required to release free radicals if the peroxide is used alone.

When treated with catalyst-accelerator combinations, standardunsaturated polyester resins show various gelation and curecharacteristics which depend on the nature of the said combination.During polymerization, resins pass-through a critical point at which theviscosity increases suddenly (gel point) then harden slowly whileundergoing an exothermic polymerization reaction. Both the gel time andthe cure exothermic heat have significant influence on the physicalproperties of the finished product as well as the practical workabilityof the resin in various applications.

In the present state of the art, cobaltous carboxylates,

I such as cobalt naphthenate, are among the most active acceleratorsavailable, but their limitations are still numerous and the gel time ofa standard polyester resin catalyzed with methyl-ethyl ketone peroxidecan merely be shortened by only 50 percent, with this accelerator. Thecure time, expressed in minutes necessary to reach the polymerizationspeak exotherm. takes well over the half hour and the performance cannotbe improved by merely increasing the metal content of the polymer. Wehave found that the di and tri hydrazine cobalt (ll) halide complexesdescribed above showed catalytic activity of the order of 20 times thatof cobalt carboxylates.

When used with acyl peroxides as primary catalyst these cobaltaccelerators have obtained polyester gel times of a few seconds. Afurther advantageous feature of these accelerators is their versatilityas gel-cure modifiers. The variation of the peroxide-accelerator ratioallows a multiple choice in gel times and cure rates of polyestersystems following the processors requirements. Finally, theseaccelerators reduce considerably the air inhibition encountered incoatings applications where the crosslinking polymerization of thinfilms is .usually affected by the presence of relatively large amountsof oxygen. It was thus possible to cure such thin films to hardness bythe mere addition of small amounts of cobalt halide hydrazine complexesas cocatalysts. The effectiveness of the cobalt hydrazine acceleratorswas observed at usage levels as low as 0.001 percent by weight of theresin and the accelerators can be used at levels as high as 5 percent oreven 10 percent (in solution or otherwise), levels at which they causeimmediate polymerizations. At higher levels the discoloration of theresin by the catalyst system is undesirable for some uses. Another areaof application where cobalt ll halide hydrazine complexes constitute asignificant improvement over existing art is the drying of paint films.They are particularly useful as primary drying catalysts for long oilalkyd paints which usually require long drying times and relatively highmetal concentrations. lt is well known that various soaps of cobaltconstitute the preferred paint driers as they are most susceptible topromote the autoxidation process by free radical induction at the sitesof unsaturation in the paint film. As pointed out before, in the case ofunsaturated polyester resins where the new catalysts overcome the airinhibition, the cobalt hydrazine complexes tend to use oxygen itself asa source of free radicals.

The superior performance observed earlier was confirmed when ketonesolutions of the cobalt hydrazine complexes were used as dryingcatalysts at similar levels of usage, varying from 0.0001 percent,usually 0.001 to percent, or more, e.g. up to percent. Furthermore, wehave found that the complexes described above show some characters ofspecificity when used as catalysts for certain aldol condensationreactions.

We have found, for instance, that the self condensation of cyclohexanonecatalyzed by the cobalt (ll)bromide dihydrazine complex [Co (ll) (N H,)]Br yields quantitative amounts of pure l-cyclohexene-Z- cyclohexanonewhereas the same condensation catalyzed with the cobalt (ll) chlorideanalog tends to promote poly condensation leading to extensive amountsof a poly cyclohexene resin.

Mesityl oxide is also obtained very easily and in high yields by selfcondensation of acetone catalyzed by various cobalt hydrazine complexcatalysts. The amount of catalyst necessary for satisfactory completionof these condensation reactions varies with the nature of the reactionand of the catalyst. In this aldol type of condensation there can beused any of the ketones previously mentioned. The catalyst can be usedto provide cobalt in the amount of 0.001 to 10 percent of the ketone.

Some homogeneous reactions such as the production of polyphenyleneoxides can be catalyzed with as little as 1 percent of a cobalt halidetrihydrazine in solution whereas in some heterogeneous conditions asmuch as 10 percent of the solid complex may be required. It is apparentfrom the results obtained, that the novel cobaltous halide trihydrazinecomplexes as well as the better known dihydrazine analogs constitute aclass of highly active catalysts useful in several diverse areas ofapplication.

In the crosslinking of olefinic polymer systems, e.g. unsaturatedpolyesters, there are included peroxides as is conventional in the art,The peroxide can be 0.05 to 5 percent, based on the polymer. Examples ofsuitable peroxides include methyl ethyl ketone peroxide, dicumylperoxide, benzoyl peroxide, cumene hydroperoxide, di (t-butyl peroxide),m-bis (alpha-t-butylperoxyisopropyl) benzene, methyl isobutyl ketoneperoxide,

' cyclohexanone peroxide, methyl tetrahydrofurane hydroperoxide, bis(4-chlorobenzoyl) peroxide, phthalyl peroxide, dilauroyl peroxide,t-butyl peracctate, diacetyl peroxide, di (2,4-dichlorobenzoyl)peroxide, dipe largonyl peroxide, 3,5-dihydroxy-3,S-dimethyl-l.2-dioxacyclopentane, t-butyl peroxybenzoate, t-butyl peroxy(Z-ethylhexanoate) 0,0-t-butyl O-isopropyl mono peroxycarbonate,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxy(2-ethylbutyrate), 2,5- dimethyl-2,5-di (Z-ethylhexanoylperoxy) hexane,di-tbutyl diperoxyphthalate, 0,0-t-butyl hydrogen monoperoxymaleate,n-butyl 4,4-bis (t-butylperoxy) valerate, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, bis-(pbromobenzoyl) peroxide.

Any of the conventional pigments can be employed in the paints such astitanium dioxide, ferric oxide, calcium oxide, zinc oxide, ochre,litharge, white lead, clays, e.g. kaolin and china clay, calciumcarbonate, silica, talc, asbestos, diatomaceous earth, basic leadcarbonate, whiting, lithopone, zinc sulfide. antimony trioxide, bariumsulfate, red lead, Spanish oxide, burnt sienna, red iron oxide, Venetianred, cadmium red.-cadmium sulfoselenide, cadmium-mercury sulfide. rawumber, burnt umber, sienna hydrated yellow iron oxide, chrome yellow,chrome orange, molybdenum orange, zinc chromate, basic zinc chromate,cadmium yellow, chrome green, chromium oxide green, iron blue,ultramarine, blue basic lead sulfate, carbon black, precipitated blackiron oxide and metallic pigments, e.g. aluminum powder.

Conventional paint solvents can be employed such as aromatic andaliphatic hydrocarbons, e.g. benzene, toluene, xylene, aromatic naphtha,mineral spirits, isooctanes, hexane petroleum ether and VM&P naphtha, as

well as water for water-based paints.

The drying accelerators of the present invention can be employed withany of the conventional drying alkyd resins and unsaturated polyesters.

The curing alkyd resins can be made from acids (or the anhydrides ifavailable) such as phthalic anhydride, isophthalic acid, trimelliticacid. pyromellitic acid. trimcsic acid, maleic anhydride, fumaric acid.azelaic acid. succinic acid. adipic acid, tetrahydrophthalic anhydride,tetrachlorophthalic anhydride, dimerized fatty acids and sebacic acidreacted with polyhydric alcohols such as glycerol, pentaerythritol,dipentaerythritol, trimethylolethane, sorbitol, trimethylolpropane,ethylene glycol, propylene glycol, neopentylene glycol and dipropyleneglycol together with drying oils such as soyabean oil, linseed oil, tungoil, dehydrated castor oil, fish oil, corn oil, perilla oil, saffloweroil, oiticica oil and cottonseed oil, as well as the acids of suchdrying oils and tall oil acids.

Unless otherwise indicated, all parts and percentages are by weight.

Typical suitable unsaturated oil or fatty acid modified alkyd resins areset forth below. They can have oil lengths of 30 to or even higher.

Alkyd A Parts 'l'all oil fatty acids 127.0 Pcntacrythritol 73.3 Ethyleneglycol 34.9 Phthalic anhydridc 145.0 Malcic anhydride 3.0 Acid No. 12

Alkyd B parts Soy-abean Oil 140.0 98% glycerol 90.0 Phthalic anhydridel45.0 Maleic anhydride 3.0 Acid No. 8

Alkyd C Alkyd D parts Suyahcan oil 25,0 Litharge 0.06 Pcntaerythritol60.0 1 10,0 Phthalic anhydride 148.0 1480 Tall oil fatty acids 260 0Ethylene glycol ]2 5 Acid No. l0 l0 Alkyd E Alkyd F Soyahean oil l32.0l75.0 Linseed oil 132.0 Dehydrated castor oil 50.0 Lithargc 0.0) 0.05Pcntacrythritol 91.0 Glycerol 83.0 Phthalic anhydridc 148.0 145.0 Malcicanhydridc 3.0 Acid No. l2 8 Alkyd G Alkyd H parts parts Tall oil fattyacids 332.0 230.0 Salllowcr oil 156.0 Lithargc 0.04 Pcntacrythritol I200I 09.0 Phthalic anhydridc I480 148.0 Acid No. l() 8 Alkyd l Alkyd J pansSoyahuan oil 366.0 Mcnhadcn oil 400.0

Phthalic unhydridc -Continued -Continued Alkyd A Polyester A Polyester BLithargc 0.08 0.10 Adipic acid l09.0 Pcntacrythritol 8L0 75.0 p-t-butylcatcchol 0.02 0.02 9871 glycerol 23.0 Acid No, 45 25 Phthulic anhydridcl45.0 Sty nc 30% of 30% of lsophthalic acid 16 composition compositionMalcic :lnhydridc 3.0 Acid N0. I2

Alkyd K Alkyd 10 As is conventional in the art, the styrene can be 20 Tuon fatty acids to 50 percent of the total composition. in place of sty-Pentaerythrito l l73.0 284.0 rene, there can be used other ethylenicallyunsaturated igf g s am :8 "(2' compounds such as diallyl phthalate,triallyl isocyanurate, acrylamide, N-t-butylacrylamide, triallyl cyang iAlkyd N urate, p-vinyl toluene. acrylonitrile, alpha methyl sty- Linsccdon 8 rene, divinyl benzene, N-vinyl pyrrolidone. methyl ac sflmowcrvil1180-0 rylate, methyl methacrylate, allyl diglycol carbonate, Lithargc0.07 0.08 h l d. l] l I pcmncrythriml 710 800 tr1met ylo propane la yether, trlmethylolpropanc Phthalic anhydridc 148.0 monoallyl ether,ally] ethers of sorbitol, pentaerythrikg z g g g" to], sucrose andglucose. Any of the polybasic acids and polyhydric alcohols employed inmaking alkyd resins can be incorporated as components in making the un-Typical examples of unsaturated polyesters, polyes- Saturated polyesterresinster resins are set f th b l I po]yesters A h h Water thlnnableunsaturatedpolyester formulatlons l, the acid and alcohol componentsprereacted to the can be used, those shown Ghosh Piltindicated acidnumber were dissolved in styrene to give 3,463,750 entlfe dlSClOSure 0fh h 18 ncome 70 percent total nonvolatiles, i.e. the styrene was rated yreference) A ypl o ula 5 that Shown m percent of the composition. Thefinal compositions also G S x mpl 1 m de from 108 parts trlmellttlcanhycontained 0,015 percent of t-but l catechol, 30 drlde, 1 18 partsphthallc anhydrlde, 108 parts trlmethylolpropane and 269 partstrimethylolpropane-diallyl ether having an acid no. of 50-52 anddissolved in 30 P l t A P I t B parts isopropanol, 60 parts of 28percent aqueous am- S 0 yes er 0 ye er nlonla, 390 parts of water and 90parts t-butyl alcohol. parts This solution at 45 percent solids ishereinafter called l.2- ropylcnc glycol I700 I700 MalEic unhydridc 1528l528 Polyester formulanon Phthalic anhydride 770 77 The followingexamples illustrate the preparation of f f 2- 2 the novel compounds ofthe present invention, their use iti g f km f as promoters for ketonealdol condensation reactions comp si i n Composition 40 and theadvantages of drying alkyd paint and varnish pulyesterc Polyester)compositions and unsaturated polyester formulations parts containing theaccelerators and catalysts of the present l.2-propylcne glycol 1700 i700invention Funlaric acid I810 603 Phthalic acid 770 2309 The standardprocedure for evaluat ng films was the yf q Q46 determination of timeuntil the film was dust free and Acid Nov 37.1 26.6 Smcmi 1 f 30% fthorough hard. These times were determined in the fol- CompositionComposition lowing manner. Within 24 to 48 hours after preparationPolyester E of the formulation, a film was applied on a polished partsplate glass panel by means ofa 0.006 inch Bird appliglywl 50 catordelivering a wet film thickness of 0.003 inch. The isophthillit. ZlCid864 film was allowed to dry in an environmental room at gy g gl 8-1constant temperature and humidity, illuminated by arf br f tificiallight and allowing 95 percent reproducibility. wmpfisilkm The dryingtimes of the film were determined by the Polyester F polyestcro improvedGardner circular drying time recorder over parts a period of 24 hours.The recorder basically consists of gl'vwl a synchronous motor with itsshaft oriented in the true Adipic Acid 1095 vertical. A pivotable armassembly is attached to this f? hd shaft and operates a counterpoisedvertical stylus coni t I'll Hvdl'thtil iliiiinit? L 0.44 05 slstmg of athermosettlng teflon sphere which does not A'Cid 1 stick to the dryingfilm. When the stylus, set in motion Stvrcnc 3071 of 3071 of IComposition Composition by the motor, no longer leaves a clear channelbut begins to rupture the dry upper layer of the film, the sur-Polvestcr H Polyester l bans face may be considered to be dust free.When the Dicthylcnc glycol 233.4 292.0 stylus no longer ruptures thefilm but moves freely on Ethylene glycol its surface, the film may beconsidered thorough Malcic unhydride l iflul hard.

EXAMPLE 1 Cobalt ll halides trihydrazine complexes were prepared by thefollowing general procedure: 0.02 mole of cobalt ll halide2,2'-bipyridine complex or cobalt ll halide azine complex was dissolvedin 50 g of dimethyl formamide. To this solution was added under strongagitation and under exclusion of air 0.06 moleof anhydrous hydrazinediluted in 50 g. of dimethyl formamide. The reaction productprecipitated readily, was filtered and dried in vacuo. The drytrihydrazine complexes are unstable when exposed to air but can bestored in ampoules under nitrogen. Table I summarizes severalpreparations of such complexes and reports the Cobalt ll trihydrazinatedibromide [Co(ll- )-(N H.,) ]Br and Cobalt l1 trihydrazinate diiodide[Co(II) (NJ- Q 11 were prepared by the procedure outlined above butcould not be analyzed because of their tendency to decompose violentlyin air. Infra-red spectrography, however, confirmed the bidentatecharacter of this ligand.

analytical data relevant to those of the compounds 15 which could behandled safely. All compounds were EXAMPLE 2 spectrographed in theinfra-red on a Perkins Elmer ln- 51 G m of obalt Il dihydrazinatedichloride (a fracord Model 337 by means of KBr wafer. All spectra knowncompound) was prepared from eob lto eh] showed a medium to strongabsorption band at 970 id d hydrazine hydrate was prepared byconvencmcharacteristic of the bidentate character of the i al ced re andsuspended in 414 grams of cyclohydrazine ligand. he'xanone and refluxedfor two hours until the reflux Phenyl hydrazine was chosen as thestandard substitemperature h d 19() 195C, At this point th tutedhydrazine in the prepa ations a t s found complex was in solution in amixture of cyclohexanone that even the relatively large size of thearomatic ring d cyclohexanone aldol oly/ onde atio products, did notprevent the formation of the octahedral com- This solution containedapproximately 4 percent cobalt plex with Cobalt ll Chl nd and was usefulas an active catalyst in curing drying oil Table I Calculated Found C0 NH Cl [Co(ll) (N l-l ',]Cl 26.1 37.1 5.3 31 4 26.04 34.95 5.1 31.4Infra-red spectra 3195 vs, 3090 vs. 2175 w,

1620 vs, 1590 vs, 1400 s, 1310 s, 1220 s, 1160 vs, 970 s, 620 m, 565 vs,518 m. [Co(lll (C l'l NH-NH -,]Cl 13.0 18.5 5.3 15 5 Carbon: Calculated:47.7%; Found: 48.8%

The cobalt ll trihydrazinate dichloride was prepared using as reactants0.02 mole of cobalt 11, 2,2- bipyn'dine dichloride complex and 0.06 moleof anhydrous hydrazine in the manner indicated supra. [It was alsoprepared by dissolving 6.4 grams (0.02 mole) of (cyclohexanone azine)cobalt ll chloride in 50 ml of dimethyl formamide and adding thereto,under strong agitation, a solution of 3.0 grams of anhydrous hydrazinein 50 m1 of dimethyl formamide. The immediately formed pale orangeprecipitate was filtered and washed with anhydrous ether. The cobalt lltrihydrazinate dichloride was obtained in quanitative yields andanalyzed Co 26.04; Cl 31.4 percent, N 33.0 percent, H

5.01 percent. (The starting cyclohexanone azine) Comodified alkyd resinsand as an activator for a crosslinkable unsaturated polyester resin.

When the refluxing is continued for several more hours above 200C,extensive polycondensation of the cyclohexanone occurs andpolycyclohexene can be precipitated by addition of hexane to thereaction mixture. The polymer was characterized by infra-red analysis.

EXAMPLE 3 2.5 g of cobalt ll bromide dihydrazine complex [Co(II) (N H]Br was suspended in 250 g of cyclohexanone and the reaction mixture wasrefluxed for 3 hours until the reflux temperature reached 275C and 23 gof water had been eliminated. The final product was distilled undervacuum to yield 184 g of pure 1-cyclohexene-2-cyclohexanone (81 percenttheory) characterized by elemental analysis. infra-red analysis andphysical properties.

EXAMPLE 4 The polymerization of 50 g of LAMlNAC 4152 (a styrene modifiedrigid polyester resin of low reactivity and of medium molecular weight.viscosity 45 poises at 77C.. manufactured by the American Cyanamid Co.),was initiatedby the addition of 0.5 g of methyl ethyl ketone peroxideand 0.5g of a 6 percent (as cobalt metal) solution of the respectivecobalt ll halide hydrazine complexes of Table 2 in cyclohexanone.

The gel time for each sample was determined at 22C on a comparativeviscosimeter capable of measuring the length of time required to reachthe point of gelation. The cure time and peak exotherm were determinedon a WEST single pen recording potentiometer. One sample wasaccelerated' with 0.5 g of cobaltous naphthenate (6 percent Co) and usedas a control.

Table-2 Min. Min. C Accelerators Gel Cure Peak Time Time Exothenn[Co(ll) (N H Cl 2 26 H6 [Co(ll) (N H Br- 20 104 [Co(ll) (N H CI: 0.2 10[Co(ll) (C,,H NHNH- Cl: 4 29 Cobalt Naphthenate l5 57 88 In place of theLAMlNAC 4152 in example 4, the use of Polyester A gives similar results.

EXAMPLE 5 The experiment of example 4 was repeated using very low levelsof the catalyst-accelerator system at 22C. The 50 g of LAMINAC 4152resin containing 0.05 g of tertiary butyl hydroperoxide and 0.1 g of abenzaldehyde solution of cobalt ll chloride dihydrazine complex [Co(ll)(N H ]Cl (6 percent Co) gelled in 16 minutes and cured in 105 minuteswhereas under similar conditions the resin containing 0.1 g of cobaltnaphthenate (6 percent Co) instead of the hydrazine complex had a geltime of several hours and did not cure after several days. Similarresults are obtained where Polyester A is substituted for the LAMINACEXAMPLE 6 I 50 g of CX 586, a high molecular weight, low reactivitystyrene modified polyester resin manufactured by the Chevron ChemicalCo., was catalyzed at 22C with 0.5 g of benzoyl peroxide and 0.5 g ofcobalt (II) chloride dihydrazinate (6 percent Co) in solution indimethyl acetamide to give a cured resin in a short period of time.Similar results are obtained when Polyester 1 is substituted for the CX586.

EXAMPLE 7 0.5 g of cobalt (ll) chloride trihydrazinate was suspended anddispersed in 50 g of LAMINAC 4152 resin. 0.5 g of benzoyl peroxide wasthen added to the system and the gel time and cure time were determinedas in example 4. A gel time of 2 hours and a cure of 4 hours wasobtained whereas a similar resin containing the peroxide but noaccelerator could not gel nor cure after 24 hours.

The dihydrazinate analog led respectively to a gel time of 3 hours and acure time of 5 hours as shown in Table 3.

No accelerator Similar results are obtained when Polyester A is substituted for LAMlNAC 4l52.

EXAMPLE 8 A typical long oil alkyd test formulation was preparedconsisting of (a) a grind containing 1265 g of titanium dioxide, 1000 gof 505- alkyd resin. (a pure soya based long oil alkyd resin havingabout 63 percent soya oil and 23 percent phthalic anhydride, Acid No. 10maximum; manufactured by the McCloskey Varnish Co.), g of Rule 66Mineral Spirit and (b) a let down containing l g of the same 505-70alkyd vehicle and 500 g of the same Rule 66" solvent. To 50 g of theabove composition was added 0.05 g of methyl ethyl ketoxime as ananti-skinning agent, and 0.4 g of a cyclohexanone solution of therespective cobalt halide hydrazine complexes reported in Table 4. (Thesolutions were standardized at a 6 percent cobalt content.) All systemswere evaluated under the standard procedure set forth above, at a roomtemperature of 32C and 30 percent humidity and compared to two similarsystems, one containing 0.4 g of cobalt octoate (6 percent Co) as drier,the other containing no drier. The results are summarized in table 4.

0.08 g of solid was used. prorated for a metal content equivalent tothat of the other systems.

The powdered cobalt ll dihydrazinate dichloride did not perform aswellas the solution because it decomposed upon standing in air.

In place ofthe 505-70 alkyd resin in example 8, the same amount of AlkydI gives similar results.

EXAMPLE 9 The drying of 50 g of the basic formulation of example 8 butcontaining no titanium dioxide pigment and no antiskinning agent wascatalyzed by the addition of 0.4 g of acetic anhydride solution (6percent Co) of the two cobalt-hydrazine complexes reported in table 5and these systems were compared to an uncatalyzed system. 1

Table 5 Dust Free Through Hard Catalysts Hours Hours No catalyst Wet Wet\Co(ll) (C H NHNH- l Br- 2.5 14 [Co(li) (C H,-,NHNH l- 22 24 'theformula [(N H In place of the 505-70 alkyd resin in example 9, therecan'be used the same amount of Alkyd H with similar results.

EXAMPLE 10 50 g of the LAMINAC 4152 polyester resin of example 4containing 0.5 g of methyl ethyl ketone peroxide as a catalyst and 0.5 gof cobalt naphthenate (6 percent Co) was applied as a 0.003 inch film ona plate glass panel and the drying time was evaluated following thegeneral procedure of example 7 at a room temperature of 22C. The filmwas never able to dry and remained tacky for several days.

A similar formulation containing 0.5 g of a benzaldehyde solution ofcobalt ll chloride dihydrazine complex (6 percent Co) instead of thecobalt naphthenate was able to dry in less than 24hours, the acceleratorhaving overcome the air inhibition process observed with the priorformulation. Furthermore, the same LAMINAC resin (50 g) containing[Co(ll) (N H ]Cl as sole catalyst (1.0 g 6 percent Co) (no peroxide)dried within 48 hours, thus showing the ability of the cobalt halidehydrazine complex to initiate free radical formations by using theatmospheric oxygen as a source.

in place of the LAMlNAC resin, Polyester A can be used with similarresults.

EXAMPLE 1 1 41.4 Grams (0.6 mole) of hydroxylamine hydrochloride weredissolved in a solution of 13 grams (0.1 mole) of cobaltous chloride in250 ml of methanol. To this solution was added, dropwise, underagitation and at room temperature, 69 grams (0.6 mole) of freshlydistilled benzalhydrazone. The agitation was maintained for 30 minutesand the precipitated purple complex was filtered, washed with ether andair dried. 33 grams of tris (hydrazine hydrochloride) cobalt II chlorideof HCl) Co(ll)]Cl was obtained (99 percent yield). The product wasstable in air and very soluble in water. Quantitative amounts ofbenzaldehyde and residual hydrazine hydrochloride were isolated bydistillation of the methanol filtrate.

The analysis of the tris (hydrazine hydrochloride) cobalt (ll) chloridewas Co 17.6 percent (theory 17.6 percent), Cl 52.5 percent (theory 52.4percent), N 24.9 percent (theory 25.1 percent), H 4.4 percent (theory4.5 percent).

What is claimed is:

1. In a process of forming a polymer by aldol condensation of a ketonethe improvement consisting essentially of heating a compositioncomprising (a) a compound having one of the formulae:

(2) [Co (11) (N H .HX);,] X and 000 (R-NHNH2)2] 2 where R is H. alkyl.aralkyl. aryl or haloaryl and X is halogen as a catalyst and (b) saidketone as solvent for said compound (a) until polymerization of theketone occurs, wherein the ketone is selected from the group consistingof acetone, methyl ethyl ketone, methyl amyl ketone, isophorone, diethylketone, di-n-propyl ketone, diisopropyl ketone, di-n-butyl ketone.diisobutyl ketone, di sec butyl ketone, di-n-amyl ketone.methyl-n-propyl ketone, pinacolone, 6-methyl-2-heptanone. methyl n-octylketone, ethyl n-butyl ketone. l-hydroxy- 2-propanone,3-hydroxy-2-butanone, diacetone alcohol, cyclobutanone, cyclohexanone,2-methy1 cyclohexanone, cycloheptanone, fenchone, acetophenone,biacetyl, acetyl propionyl, acetyl acetone, mesityl oxide andhexanone-3.

2. A process according to claim 1 wherein the catalyst is present in anamount to provide 0.001 to 10 percent of cobalt based on the ketone.

3. A process according to claim 1 wherein compound (a) has formula (2).

4. A process according to claim 1 wherein the ketone is cyclohexanone.

5. A process according to claim 4 wherein R is hydrogen and X ischlorine.

6. A process according to claim 1 wherein compound (a) has formula (1).

7. A process according to claim 6 wherein R is gen. v

8. A process according to claim 1 wherein compound (a) has formula (3).

9. A process according to claim 8 wherein R is hydrogen.

hydro-

1. IN A PROCESS OF FORMING A POLYMER BY ALDOL CONDENSATION OF A KETONETHE IMPROVEMENT CONSISTING ESSENTIALLY OF HEATING A COMPOSITIONCOMPRISING (A) A COMPOUND HAVING ONE OF THE FORMULAE: (1) (CO (II)(R-NHNH2)3) X2 (2) (CO (II) (N2H4.HX)3) X2 AND (3) (CO (II) (R-NHNH2)2)X2 WHERE R IS H. ALKYL, ARALKYL, ARYL OR HALOARYL AND X IS HALOGEN AS ACATALYST AND (B) SAID KETONE AS SOLVENT FOR SAID COMPOUND (A) UNTILPOLYMERIZATION OF THE KETONE OCCURS, WHEREIN THE KETONE IS SELECTED FROMTHE GROUP CONSISTING OF ACETONE, METHYL ETHYL KETONE, METHYL AMYLKETONE, ISOPHORONE, DIETHYL KETONE, DI-N-PROPYL KETONE, DIISOPYROPYLKETONE, DI-N-BUTYL KETONE, DIISOBUTYL KETONE, DI SEC BUTYL KETONE,DI-N-AMYL KETONE, METHYL-N-PROPYL KETONE, PINACOLONE,6-METHYL-2HEPTANONE, METHYL N-OCTYL KETONE, ETHYL N-BUTYL KETONE1HYDROXY-2-PROPANONE, 3-HYDROXY-2-BUTANONE, DIACETONE ALCOHOL,CYCLOBUTANONE, CYCLOHEXANONE, 2-METHYL CYCLOHEXANONE, CYCLOHEPTANONE,FENCHONE, ACETOPHENONE, BIACETYL, ACETYL PROPIONYL, ACETYL ACETONE,MESITYL OXIDE AND HEXANONE-3.
 2. A process according to claim 1 whereinthe catalyst is present in an amount to provide 0.001 to 10 percent ofcobalt based on the ketone.
 3. A process according to claim 1 whereincompound (a) has formula (2).
 4. A process according to claim 1 whereinthe ketone is cyclohexanone.
 5. A process according to claim 4 wherein Ris hydrogen and X is chlorine.
 6. A process according to claim 1 whereincompound (a) has formula (1).
 7. A process according to claim 6 whereinR is hydrogen.
 8. A process according to claim 1 wherein compound (a)has formula (3).
 9. A process according to claim 8 wherein R ishydrogen.